Radiation-induced emulsion polymerization of vinyl acetate and styrene

Studies have been made of the γ-induced emulsion polymerization of styrene and comparisons made with chemically initiated emulsion polymerization. The polymerization proceeded smoothly to high conversions at 0 and 60°C, the reaction showing a high G (monomer) value. Complete conversions were obtained with total doses of less than 0.05 Mrad. In accordance with the behavior expected of systems having a constant rate of initiation, the molecular weight was found to decrease with decreasing temperature. The molecular weight and particle size distributions were narrower than those obtained in chemically initiated emulsion polymerizations at the same temperature. The radiation-induced emulsion polymerization of vinyl acetate proceeded smoothly at temperatures in the range 0–50°C to give polymers of much higher molecular weight than these obtained from chemically initiated polymerizations at the same temperature. Complete conversion was attained after a dose of 0.02 Mrad for latices approaching 50% solids. The elimination of ionic endgroups in the poly(vinyl acetate) radicals tends to drive the polymerization from the aqueous phase, resulting in faster rates and higher molecular weights than are obtained from chemically initiated systems. Rates of polymerization were found to be independent of temperature and the molecular weight of the polymer to be independent of dose rate. Latices of poly(vinyl acetate) of high solids content were evaluated for latex and film properties and found to have improvements over commercially available samples in both areas, especially in clarity of film and scrub resistance. A number of acrylate and maleate esters were copolymerized with vinyl acetate in a radiation-initiated emulsion system. High molecular weight copolymers were produced after low dose.     

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene. V. Formation of acid and its effect

In the radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene, it was found that hydrofluoric acid (HF) is formed in the course of polymerization. The amount of HF formed increased linearly with the irradiation time in all cases. The rate of HF formation was maximum at 0.3 wt-% emulsifier and increased linearly with tetrafluoroethylene content in the monomer mixture. On the other hand, the conversion and the molecular weight decreased remarkably by addition of 0.1M HF. The particle diameter of copolymer obtained in the presence of HF was larger than that obtained in the HF-free system. On the contrary, the number of polymer particles was less than that obtained in the HF-free system. The decrease in the conversion and the molecular weight was attributed mainly to the conversion of part of ammonium perfluorooctanoate to perfluorooctanoic acid by formation of acid or addition of acid.     

Plasma polymerization of tetrafluoroethylene

The plasma polymerization of C₂F₄ was carried out in both continuous wave and pulsed rf discharges to establish the effects of reaction conditions on the kinetics of polymer deposition and the polymer structure. ESCA spectra of the polymer show evidence for ? CF₃, ? CF₂, and ? CH₂? groups. Under conditions favoring low deposition rates, the dominant functional group is ? CF₂? . At higher deposition rates the concentration of ? CF₂? groups is reduced and a more crosslinked polymer is produced. Both polymer deposition rates and polymer structures were essentially identical when using continuous wave and pulsed rf discharges.     

Explosion of tetrafluoroethylene during nonisothermal polymerization

On the basis of dimerization kinetics and experimental data on thermal explosion we determine conditions for ignition of tetrafluoroethylene on a hot wall. A mathematical model of nonisothermal polymerization on a plane wall and in a cavity which takes into account heat removal to the wall and to the gas phase is proposed. The conditions for explosion hazard situations are established and expressions for the induction time are obtained. Saint Peterburg. Translated from Fizika Goreniya i Vzryva, Vol. 29, No. 5, pp. 56–62, September–October, 1993.     

Emulsifier-free emulsion polymerization of tetrafluoroethylene by radiation. IV. Effects of additives on polymer molecular weight

Poly(tetrafluoroethylene) (PTFE) of high molecular weight, 4.5 × 10⁷, was incidentally obtained at earlier study of an emulsifier-free emulsion polymerization of tetrafluoroethylene by radiation. In order to clarify this phenomenon, the effects of additives, in particular radical scavengers, on the molecular weight of PTFE and its polymerization behavior were studied. It was found that the molecular weight of PTFE is increased by the addition of hydroquinone, benzoquinone, α-pinene, dl-limonene, and ethylenediamine but is decreased by oxygen and triethylamine. A PTFE latex with molecular weight higher than 2 × 10⁷ was obtained in the presence of hydroquinone. It is concluded that additives such as hydroquinone and benzoquinone, which rapidly scavenge the primary radicals (OH·, H·, and e_aq^?) in the aqueous phase but not the growing polymer radicals in PTFE particles, are most effective in increasing the molecular weight.     

Radiation-induced solid state polymerization

The literature on radiation-induced solid state polymerization has been increasing exponentially in the last five years. Major advances have been made in retention of crystalline morphology during polymerization, in stereospecific polymerization, in modification of reactivity ratios in copolymerization and in molecular weight control of the product. However, at the present time, no commercial products have resulted from the study of radiation-induced solid state polymerization. Chemically induced polymerization techniques have been keeping abreast of this explosive development in the solid state polymerization field and have up to this time precluded the use in industry of solid state polymerization. The major potential at the present time appears to be in the area of producing fibers without additional processing.     

Radiation-induced emulsion polymerization of vinyl acetate in a pilot plant reactor I. Recycle flow reactor

A number of successful radiation polymerization of vinyl acetate in emulsion have been carried out in a modular stainless steel flow pilot plant. In a recycle mode, the system was utilized for extremely accurate kinetic measurements and experimental verification of model restrictions such as plug flow, lack of post irradiation effects and differential reactor behavior. Experimental conditions were explored to minimize contaminant, primarily oxygen, inhibition, and the tendency for this formulation, essentially an adhesive, to build up on the reactor walls. Industrial scaleup of such a prototype system appears attractive.     

Plasma polymerization of tetrafluoroethylene in a field-free zone

Plasma polymerization of tetrafluoroethylene by itself and mixed with inert gases has been studied in the field free zone inside a Faraday cage. The chemical structure was analyzed by ESCA, revealing both linear and branched products. Linear products are formed by less energetic plasmas and at low monomer residence times. Lower energy plasmas result from the use of lower powers and lower percentages of helium in the feed. Production of linear products under these conditions is probably due to lower rates of free radical and metastable formation in the plasma. Through a combination of kinetic and mass transfer effects, shorter monomer residence times under high flow rates and within short distances from the front edge of the electrode give rise to a lower concentration of free radicals at the electrode surface, producing a more linear polymer. Linear products were also formed at very high powers. This latter result is quite unexpected and is probably due to rapid gas phase polymerization. The chemical structure was not affected significantly by the substrate temperature or by hydrodynamics in this work. All of the evidence indicates that the gases were well mixed in the reaction zone for the range of process variables and for the gases studied. The deposition rate was also studied as a function of the reaction conditions. It was affected by the concentration of free radicals, the concentration of the monomer, and the substrate temperature. The observed deposition rate profile across the electrode is consistent with mass transfer and kinetic considerations governing free radical and monomer concentrations on the electrode surface. The deposition rate is greater at the lower substrate temperature used, probably due to enhanced adsorption process.     

乳液聚合方法研究进展

乳液聚合方法具有各方面的优点和广泛的应用范围,因此,受到人们的广泛关注。本文介绍了乳液聚合的优缺点,并着重介绍了一些新的乳液聚合方法及其原理、特点、应用以及中外最新的一些研究成果。     

Radiation-induced seeded copolymerization of tetrafluoroethylene with propylene. II. Kinetic analysis

The radiation-induced seeded copolymerization of tetrafluoroethylene with propylene was kinetically analyzed by assuming that growing radical in polymer particle is deactivated by degradative chain transfer to propylene and/or by recombination with newly entered radical which grows for a while before recombination. Apparent rate constant of initiation is 2.6 × 10^?9 mole/liter rad independent of the monomer composition in polymer particles. Apparent rate constant of propagation lies in the range of 10⁵ hr^?1 increasing with tetrafluoroethylene fraction. Change in apparent rate constant of chain transfer with propylene fraction suggests that first-order termination by radical occlusion or radical escape to aqueous phase may occur simultaneously with the degradative chain transfer. Average number of radical in a particle is found to increase with dose rate and levelled off at the value of 0.9. The higher value above 0.5 is explained by Trommsdorff effect. The dose rate exponent of average number of radical changes from 1 to 0 with increasing dose rate. This change is consistent with the dose rate effect on the polymerization rate under the constant number of polymer particles.     

Fiber making directly from poly(tetrafluoroethylene) emulsion

Poly(tetrafluoroethylene) (PTFE) fiber with a superior mechanical property was prepared directly from its emulsion by the novel manufacturing process. The PTFE emulsion turned into a paste when a high shear flow was applied and the paste was extruded through a nozzle into a strand consisting of fine PTFE particles. The diameter of the strand was reduced stepwise by applying the die-drawing process through a conical die at a low temperature. The strand was further die-drawn down at elevated temperatures into fine PTFE fibers with a highly oriented crystalline structure. The crystalline orientation factor of the PTFE fiber reached very close to unity. Although the fibers obtained have a very high tensile modulus, the tensile strength was not as high as that expected from the crystalline orientation, suggesting that the presence of some defects in the PTFE fiber formed in the instantaneous deformation.     

Radiation-induced grafting of acrylic acid onto expanded poly(tetrafluoroethylene) membranes

Expanded poly(tetrafluoroethylene) (ePTFE) is currently being applied in facial reconstruction surgery. One requirement for the use of ePTFE membranes in soft tissue replacements is establishment of a well-bonded interface with the surrounding bone. However, ePTFE is classified as bioinert, thus lacking in biomimetic properties which may result in poor osseointegration at the bone–implant interface. Thus, the introduction of functional groups onto the polymer surface was carried out in the current study using radiation induced grafting of acrylic acid (AA) yielding graft yields of up to 40%. This resulted in reducing the hydrophobicity (advancing contact angle reduced from 116 to 92°). XPS revealed that the grafted PAA was highly crosslinked. The effects of grafting conditions (dose, monomer concentration, as well as solvent) on the grafting outcome were evaluated. Grafting of tertbutyl acrylate (tBA) was investigated but low graft yields were obtained and this was shown to be unaffected by the solvent used during the grafting process. The mechanical properties of the AA grafted membranes were altered significantly and were dependent on the testing conditions (wet or dry).     

Silicone-stabilized nonaqueous emulsion polymerization

Stable dispersions are prepared by free-radical polymerization of methyl methacrylate in aliphatic hydrocarbons containing poly(dimethylsiloxane) modified with mercaptoalkyl side groups. The particles are pictured as being stabilized by a protective layer of solvated poly(dimethylsiloxane). Some important features of the polymerization are described.     

有机硅氧烷 -丙烯酸酯乳液聚合研究进展

介绍了有机硅-丙烯酸酯乳液聚合物的3种制备方法及各种乳液的特点,对各种乳液的近期研究成果进行了总结。     

种子乳液聚合制备MCPU-PMMA复合乳液

本文采用改性蓖麻油合成了软段中含不饱和双键的阴离子聚氨酯水分散液（MCPU），将其作为可聚合乳化剂和种子成分同甲基丙烯酸甲酯（MMA）进行共聚，制得了MCPU－PMMA复合乳液。1HNMR谱图显示MCPU中含有双键结构,共聚后双键消失。通过考察单体转化率和复合乳液平均粒径、凝胶量及成膜耐水及甲苯性探讨了影响种子乳液聚合的多种因素：采用过硫酸钾作为引发剂，单体转化率高，乳液粒径小，成膜耐水及甲苯性好；反应的表观活化能Ea为164.86kJ/mol，反应温度控制在70℃较适宜；聚合反应速率Rp∝［I］1.0856，引发剂用量宜控制在聚合有效组份总质量的0.5％。     

溶液聚合和乳液聚合的生产工艺流程

<正>根据合成条件(包括单体形状、介质物态)的不同,合成橡胶的聚合可分为本体聚合、气相聚合、乳液聚合及溶液聚合等四种。本体聚合虽具有所得聚合物纯度高,无需脱气、脱水、后处理等优点,但散热困难、聚合速度慢,对橡胶合成并不适用(但适用     

The effects of hydrogen on the plasma polymerization of tetrafluoroethylene

A study was made of the effects of hydrogen containing additives on the polymerization of tetrafluoroethylene in a radiofrequency low pressure plasma. The addition of ethylene and molecular hydrogen were found, under certain circumstances, to significantly increase the rate of polymer deposition. This effect is ascribed to the release of hydrogen atoms from the additive, which enhance the formation of fluorocarbon-free radicals and scavenges fluorine atoms. ESCA (electron spectroscopy for chemical analysis) spectra of the deposited films show that upon addition of hydrogen to the monomer, the F/C ratio of the film decreases and the H/C ratio rises. Hydrogen addition also influences the extent of crosslinking—a decrease being observed at low discharge power and an increase being observed at high discharge power.     

Radiation-induced polymerization of styrene at high dose rates

A kinetic equation was derived for the radiation-induced polymerization of styrene under the assumption that both radical and cationic polymerizations take place concurrently throughout the whole range of the dose rate of radiation and the water content of the styrene. The equation enables one to calculate rates of the total, radical, and cationic polymerization at a given dose rate and water content and agrees satisfactorily with experimental results, which cover dose rates from 4.2 × 10 to 2.1 × 10⁵ rad/sec and water contents from 3.2 × 10^?3 to 3.5 × 10^?2 mol/l. Experimental estimation of the contribution of radical and cationic mechanisms was done by GPC curves of polymers obtained under various conditions. When the contribution of ionic mechanism is expressed in weight percent, it changes from 0% to 100% in the range of the experiment; on the other hand, if it is expressed in mole percent, it is independent of the dose rate and remains constant throughout the whole range of the experiment.     

Inifer surfactants in emulsion polymerization

Thiol-ended non-ionic surfactants, used in combination with t-butyl hydroperoxide are components of a redox system able to initiate the emulsion polymerization of styrene, as well as control the molecular weight by transfer. Most of the surfactants remain as side products in the water phase, while multimodal molecular weight distributions of polymer are observed depending on the structure of the surfactant, the conversion of the monomer and the process used for feeding the reactor. The maximum incorporation yield of these reactive surfactants in the polymer is around 40%.     

Crosslinking kinetics in emulsion polymerization

Network formation in free-radical polymerization is investigated both from experimental and theoretical points of view. In a bulk free-radical crosslinking copolymerization, the radical concentration increases significantly due to a decrease in the bimolecular termination rate. Some fraction of radicals is trapped during the course of network formation, and the reactivity of the radicals in liquid state is completely different from that in solid state (trapped radicals) in terms of both propagation and termination. In emulsion crosslinking polymerization, the crosslinking density tends to be fairly high even from the start of the polymerization. The crosslinking density development is substantially different from that in bulk and solution polymerizations, in which the crosslinking density increases with time, at least in the earlier stages of polymerization. Due to the elastic contribution of free energy change, the monomer concentration in the polymer particles is lower than for linear emulsion polymerizations as long as the monomer droplets exist, resulting in an enhanced tendency toward crosslinking reactions.